Acidic lipid alkyl carbonates



United States Patent 3,405,148 ACIDIC LIPID ALKYL CARBONATES James E. Thompson, Colerain Township, Hamilton County, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Dec. 17, 1964, Ser. No. 419,182 Claims. (Cl. 260-4043) ABSTRACT OF THE DISCLOSURE New acidic lipid alkyl carbonates having the formula wherein R is an alkyl group; and R is an acidic lipid acyl residue derived from a condensation product of a fatty .acid and a hydroxy carboxylic acid containing 3-6 carbon atoms, or a condensation product of a dicarboxylic acid containing 3-6 carbon atoms having no hydroxyl groups and fatty alcohol or fatty ester with free hydroxyl groups. The compounds are useful as bakery additives, and have Wetting, emulsifying and detergent properties.

This invention relates to new organic compounds and, more particularly, to novel acidic lipid alkyl carbonates having utility as additives for bakery products such as bread, cakes, pies, doughnuts, cookies, icings, fillings, and the like products prepared from emulsions comprising water, fats, proteins and/or carbohydrates.

The volume, texture, and eating qualities of many bakery products are dependent upon the interaction of various ingredients during the mixing operation in which a dough, batter, or other emulsion is formed and the stabilization during subsequent baking and/ or storage of the bakery product. Many attempts have been made to improve the emulsion characteristics of bakery products by incorporating therein small amounts of various additives which are able to affect the colloidal properties of the proteinaceous, and/ or amylaceous, and/or oleaginous bakery constituents. Although a number of the conventional additives such as lecithin and the partial glycerides of higher fatty acids have been found to be useful emulsifiers in bakery products, these emulsifiers have not provided the desired air incorporation and foam stability.

It is an object of this invention to provide a new group of organic compounds which are useful for improving air incorporation and foam stability in doughs, batters, and other bakery emulsions.

Other objects and advantages will be apparent from the disclosure herein.

The objects of this invention are accomplished with a group of novel compounds having the general formula wherein R is selected from the group consisting of alkyl radicals having from 1 to 30 carbon atoms, phenyl, benzyl, and tolyl radicals, and wherein R is the acyl residue of an acidic lipid selected from the group consisting of (a) A condensation product of a fatty acid having from 12 to 22 carbon atoms with a hydroXy-polycarboxylic acid having from 1 to 4 hydroxyl groups, said hydroxy-polycarboxylic acid containing 3 to 6 carbon atoms,

3,405,148 Patented Oct. 8, 1968 ice said condensation product having at least one free carboxyl group per molecule;

(b) A condensation product of a dicarboxylic acid having no hydroxyl groups and containing from 4 to 6 carbon atoms with a straight chain aliphatic ot,w-di0l monoester of fatty acid, said diol containing from 3 to 5 carbon atoms, said fatty acid having from 12 to 22 carbon atoms, .and said condensation product having at least one free carboxyl group per molecule;

(c) A condensation product of a dicarboxylic having no hydroxyl groups and containing from 4 to 6 carbon atomswith a straight chain aliphatic primary-secondary diol monoester of fatty acid, said diol containing from 3 to 5 carbon atoms, said fatty acid having from 12 to 22 carbon atoms, and said condensation product having at least one free carboxyl group per molecule;

(d) A condensation product of a dicarboxylic acid having no hydroxyl groups and containing from 4 to 6 carbon atoms with a partial fatty acid glyceride containing from one to two fatty acid radicals having from 12 to 22 carbon atoms and from zero to one fatty acid radical having from 2 to 6 carbon atoms, said condensation product having at least one free carboxyl group per molecule;

(e) A condensation product of fatty acid containing from 12 to 22 carbon atoms with an w-hydroxy-monocarboxylic acid having from 3 to 6 carbon atoms;

(f) A condensation product of a dicarboxylic acid having no hydroxyl groups and containing from 4 to 6 carbon atoms with a straight chain fatty alcohol having from 12 to 22 carbon atoms, said condensation product having at least one free carboxyl group per molecule; and

(g) A condensation product of a dicarboxylic acid having no hydroxyl groups and containing from 4 to 6 carbon atoms with a diethylene glycol monoester of fatty acid, said fatty acid having from 12 to 22 carbon atoms and said condensation product having at least one free carboxyl group per molecule.

For improving the air incorporation and foam stability of doughs, batters, and other bakery emulsions it is preferable that R in the above formula be an alkyl radical having 2 to about 6 carbon atoms.

The novel acidic lipid alkyl carbonates of this invention are preferably prepared by reaction of the triethylammonium salts of an acidic lipid condensation product having the formula of products (a) through (g) with suitable alkyl or aryl chloroformates at low temperatures, such as from about 0 C. to about 25 C. Synthesis of these new compounds can also be accomplished with salts other than the triethylammonium salts, for example, the sodium or potassium salts.

The acidic lipid residue (R') in the above formula is derived from acidic lipid condensation products (a) to (g), above, which must contain at least one longchain or higher alkyl radical having from about 12 to about 22 carbon atoms and at least one free carboxyl group per molecule. These long chain radicals can be derived, for example, from lauric, myristic, palmitic, stearic, oleic, linoleic, linolenic, arachidic, behenic, and erucic acids or from the corresponding long-chain fatty alcohols. A preferred long chain alkyl radical has from abuot 16 to about 18 carbon atoms. The free carboxyl group of the acidic lipid condensation product supplies the group which is attached to the (R') group in the above formula.

In the above acidic lipid condensation products, the

hydroxy-polycarboxylic acids in (a) having from 1 to 4 hydroxyl groups and containing from 3 to 6 carbon atoms include, for example, malic, tartaric, citric, citramalic, trihydroxy glutaric, mucic, saccharic, and mannosaccharic acids. The dicarboxylic acids in (b), (c), (d), (f) and (g) having no hydroxyl groups and containing from 4 to 6 carbon atoms include, for example, succinic, glutaric, and adipic acids. The a,w-diOlS in (b) include, for example, 1,3-propanediol, 1,4-butanediol and 1,5-pentanediol. The preferred primary-secondary diol in (c) is propylene glycol. The partial glycerides in (d) include, for example, monoand distearin, monoand diolein, dilaurin and monoacetyl monobehenin. The a:- hydroxy-monocarboxylic acids in (e) include, for example, 3-hydroxypropanoic acid, 4-hydroxybutanoic acid, S-hydroxypentanoic acid and 6-hydroxyhexanoic acid.

The acidic lipid condensation products in (a) through (g) are prepared by reacting appropriate hydroxyl-containing compounds with appropriate carboxyl-containing compounds by conventional esterification reaction methods known to those skilled in the art. Suitable detailed procedures are described, for example, in the co-pending applications of James Bruce Martin, Ser. Nos. 321,292 and 321,331, filed Nov. 4, 1963 now U.S. Patents 3,350,- 413 and 3,371,102, respectively.

Although it is not desired to be bound by theory, it is believed that the mechanism by which the novel acidic lipid alkyl carbonates of this invention act in cake batters and other bakery emulsions is by direct chemical reaction with other batter constituents, such as protein, which, in turn, leads to the etfective stabilization of the batter, particularly at high temperatures such as ordinary baking temperautres. However. Irrespective of the mechanism by which these compounds function in the batter, it has been found that the addition of about 0.1% to about 15%, and preferably about 0.1% to about 4%, by weight of the bakery product, of one or more of these com pounds to the batter system increases the air incorporating properties of conventional emulsifiers and stabilizes the cake batter against shrinkage during baking and subsequent cooling of the cake. These stabilization properties give rise to improved cakes of high volume and fine texture.

The following examples further illustrate the new organic compounds of this invention and their methods of preparation but the invention is not limited to these specific examples; many other examples will become readily apparent to the person skilled in the art after reading this specification and the appended claims. All

percentages and parts are by weight unless otherwise The synthesis of each of the following acidic lipid alkyl carbonates was accomplished in essentially the same manner with necessary variations as indicated. In a round bottomed flask equipped with a thermometer, a stirrer, an addition funnel and a nitrogen inlet were placed equimolar (or equivalent) amounts of acidic lipid condensation product and triethylamine dissolved in an appropriate amount of anhydrous ether or a mixture of anhydrous ether and anhydrous benzene as indicated. This solution was cooled to C.-15 C. in an ice bath and then an equimolar (or equivalent) amount of ethyl chloroformate was added dropwise at such a rate that the temperature did not rise above 15 C. After the chloroforrnate had been added, the reaction mixture was stirred for an additional 15-60 minutes at 0 C.-15 C. and was then filtered to remove the triethylamine hydrochloride precipitate. Evaporation of the solvent at room temperature under vacuum gave the acidic lipid alkyl carbonate.

(a) Treatment of 13.6 g. (0.020 mole) of tartaric distearate, 4.1 g. (.040 mole) of triethylamine and 4.4 g. (0.040 mole) of ethyl chloroformate in a total of 400 ml.

of ether in the above manner gave 11.2 g. (68%) of 2,3- distearoyloxysuccinyl bis-(ethyl carbonate).

(b) In the same manner as in (a), 22.1 g. (0.050 mole) of stearoyl propylene glycol hydrogen succinate, 5.1 g. (0.050 mole) of triethylamine and 5.4 g. (0.050 mole) of ethyl chloroformate gave 20.7 g; (81%) of stearoyl propylene glycol succinatyl ethyl carbonate.

(c) Treatment of 7.2 g. (0.010 mole) of distearin hydrogen succinate, 1.0 g. (0.010 mole) of triethylamine and 1.1 g. (0.010 mole) of ethyl chloroformate in a mixture of ml. of benzene and 60 ml. of ether in the above manner gave distearin succinatyl ethyl carbonate.

((1) In the same manner as in (c), 11.1 g. (0.030 mole) of 4-stearoyloxybutyric acid, 3.1 g. (0.030 mole) of triethylamine and 3.3 g. (0.030 mole) of ethyl chloroforrnate gave 10.8 g. (81%) of 4-stearoyloxybutyryl ethyl carbonate.

The acidic lipid alkyl carbonate structure of the compounds prepared in Example I was confirmed by infrared spectra analysis.

Example II In a manner similar to Example I(c), octadecyl glutaratyl ethyl carbonate was prepared from 4.3 g. (0.01 mole) of octadecyl hydrogen glutarate, 1.0 g. (0.010 mole) of triethylamine and 1.1 g. (0.010 mole) of ethyl chloroformate. Similarly, using the appropriate proportions of reactants, stearoyl propylene glycol adipatyl ethyl carbonate was prepared from stearoyl propylene glycol hydrogen adipate; stearoyloxysuccinyl bis-(ethyl carbonate) was prepared from malic stearate; stearoyl dihydroxy ethyl ether succinatyl ethyl carbonate was prepared from stearoyl dihydroxy ethyl ether hydrogen succinate; stearoyl 1,3-propanedi0l succinatyl ethyl carbonate was prepared from stearoyl 1,3-propanediol hydrogen succinate; and dipalmitin succinatyl ethyl carbonate was prepared from dipalmitin hydrogen succinate. Methyl, stearyl, phenyl, benzyl, and tolyl chloroformates can be substituted for an equivalent amount of ethyl chloroformate in the above example to give corresponding carbonates. Myristyl and behenyl radicals can be substituted for equivalent amounts of palmityl and stearyl radicals in the acidic lipid residues of the carbonates of the above example to give corresponding carbonates.

Example 111 The effectiveness of the compounds of this invention as shortening additives and as cake batter stabilizers is illustrated with a liquid vegetable oil shortening and with both low-ratio and high-ratio white and yellow cake mixes employing the distearin succinatyl ethyl carbonate of Example 1(c).

(a) A fluid shortening was prepared by uniformly mixing together the following components in the stated amounts:

Components: Parts by weight Refined, bleached and deodorized liquid cottonseed oil 84 Propylene glycol stearate (approximately /2 each monoand diesters) 14 Distearin succinatyl ethyl carbonate 2 This shortening is useful for the commercial and household preparation of bakery products such as bread, cakes, pies, doughnuts, cookies, icings, fillings, and the like products made from emulsions comprising water, fats, proteins and/or carbohydrates. Parts (b), (c), (d) and (e) below illustrate low-ratio White and yellow cake mixes and highratio quick method white and yellow cake mixes, respectively, using the liquid shortening of part (a) for the preparation of high volume cakes.

(b) White cakes were prepared from the following ingredients:

The shortening and egg whites were added to a mixture of the dry ingredients and then 150 ml. of water was mixed in with an electric'mixer at 500 rpm. for 3 minutes. 440 grams of batter was placed in an 8-inch pan and baked in an oven at 375 F. for about 25 minutes. The batter density was 0.55 g./cc. and the cake volume minutes after removal of the cake from the oven was 1445 cc./440 g. of batter. The cake had a fine texture.

(c) In the same manner, a yellow cake mix produced a batter density of 0.57 g./cc. and a cake volume of 1485 cc./440 g. of batter.

(d) A high-ratio quick method White cake was prepared from the following ingredients:

Ingredients: Part by weight, grams Cake flour 107.0 Granulated sugar (sucrose) 133.0 Salt (NaCl) 2.5 Double-acting baking powder 6.7 Shortening 47.5 Whole milk 130.0 Egg whites (fresh) 60.0 Flavor 2.5

The shortening and other liquid ingredients (milk and egg whites) were added simultaneously to all of the dry ingredients and mixed with a Sunbeam table model electric mixer at 50 r.p.m. for a total of 4 minutes. 400 grams of batter was placed in an 8-inch pan and baked in an oven at 365 F. for about minutes. The batter density was 0.54 g./cc. and the cake volume 20 minutes after removal of the cake from the oven was 1450 cc./400 g. of batter.

(e) In the same manner, a high-ratio quick method yellow cake produced a batter density of 0.54 g./cc. and a cake volume of 1440 cc./400 g. of batter.

Example IV The ettectiveness of several other examples of the compounds of this invention in high-ratio quick method white cakes is illustrated in this example. For purposes of comparison, the control cake which did not contain the acidic lipid alkyl carbonate had a volume of 930 cc./400 g. of batter.

(a) 2% stearoyl propylene glycol succinatyl ethyl carbonate in the Shortening component produced a cake volume of 1490 cc./400 g. of batter.

(b) 2% stearoyl propylene glycol adipatyl ethyl carbonate in the shortening component produced a cake volume of 1405 cc./400 g. of batter.

(c) 2% 4 stearoyloxybutyryl ethyl carbonate in the shortening component produced a cake volume of 1515 cc./400 g. of batter.

(d) 2% stearoyloxysuccinyl bis (ethyl carbonate) in the shortening component produced a cake volume of 1455 cc./400 g. of batter.

(e) 2% 2,3 distearoyloxysuccinyl bis (ethyl carbon ate) in the shortening component produced a cake volume of 1405 cc./400 g. of batter.

.(f) 1% octadecyl glutaratyl ethyl carbonate in the shortening component produced a cake volume of 1475 cc./400 g. of batter.

Similar high volume cakes are obtained when the other acidic lipid alkyl carbonates of Examples I and II are substituted for the acidic lipid alkyl carbonates of Example IV.

In addition to their use in bakery emulsions the novel compounds of this invention are desirable acylating agents for forming esters having surface-active properties such as Wetting, emulsifying, and detergent properties. As examples of such acylating properties, stearoyl propylene glycol succinatyl carbonate was used to synthesize stearoyl propylene glycol succinatyl glycerol by the acylation of glycerol; distearin succinatyl ethyl carbonate was used to synthesize distearin succinatyl xylitol by the acylation of xylitol. As further examples of the usefulness of the compounds of this invention as acylating agents for the preparation of such surface-active esters, distearin glutaratyl ethyl carbonate can be used to synthesize distearin glutaratyl glycerol and'octadecyl adipatyl phenyl carbon ate can be used to synthesize octadecyl adipatyl glycerol by the acylation of glycerol.

Other examples will be apparent to the person skilled in the art and all such variations are included within the scope of this invention as set forth in this specification and the claims appended hereto.

What is claimed is:

1. An acidic lipid alkyl carbonate having the formula wherein R is selected from the group consisting of alkyl radicals having from 1 to 30 carbon atoms, phenyl, benzyl, and tolyl radicals and wherein R is the acyl residue of an acidic lipid selected from the group consisting of (a) a condensation product of a fatty acid having from 12 to 22 carbon atoms with a hydroxypolycarboxylic acid having from 1 to 4 hydroxyl groups, said hydroxy-polycarboxylic acid containing 3 to 6 carbon atoms, said condensation product having at least one free carboxyl group per molecule;

(b) a condensation product of a dicarboxylic acid having no hydroxyl groups and containing from 4 to 6 carbon atoms with a straight chain aliphatic a,w diol monoester of fatty acid, said diol containing from 3 to 5 carbon atoms, said fatty acid having from 12 to 22 carbon atoms, and said condensation product having at least one free carboxyl group per molecule;

(0) a condensation product of a dicarboxylic acid having no hydroxyl groups and containing from 4 to 6 carbon atoms with a straight chain aliphatic primary-secondary diol monoester of fatty acid, said diol containing from 3 to 5 carbon atoms, said fatty acid having from 12 to 22 carbon atoms, and said condensation product having at least one free carboxyl group per molecule;

(d) a condensation product of a dicarboxylic acid having no hydroxyl groups and containing from 4 to 6 carbon atoms with a partial fatty acid glyceride containing from one to two fatty acid radicals having from 12 to 22 carbon atoms and from zero to one fatty acid radical having from 2 to 6 carbon atoms, said condensation product having at least one free carboxyl group per molecule;

(e) a condensation product of fatty acid containing from 12 to 22 carbon atoms with an (0- hydroxy monocarboxylic acid having from 3 to 6 carbon atoms;

(f) a condensation product of a dicarboxylic acid having no hydroxyl groups and containing from 4 to 6 carbon atoms with a straight chain fatty alcohol having from 12 to 22 carbon atoms, said condensation product having at least one free carboxyl group per molecule; and

(g) a condensation product of a dicarboxylic acid 10. An acidic lipid alkyl carbonate having the formula having no hydroxyl groups and containing from 4 to 6 carbon atoms with a diethylene glycol o monoester of fatty acid, said fatty acid having R -'O ""OCHICH3 from 12 to 22 carbon atoms and Said condensa' 5 wherein R" is an acyl residue derived from an acid setion product having at least one free carboxyl pasted fr h group consisting f g p p r molficule- (1) 2,3-distearoyloxy succinic acid mono(ethyl carbon- 2. A compound of claim 1 wherein R is an alkyl radical ate) having from 2 to 6 carbon atoms. (2) stearoyl propylene glycol hydrogen succinate 3. A compound of claim 1 wherein R contains at 10 (3) distearin hydrogen succinate least one alkyl radical having from 16 to 18 carbon 4-stealoyloxybutfic acid atoms. .(5) octadecyl hydrogen glutarate 4. A compound of claim 1 wherein R is an alkyl radical (6) Stearoyl Propylene g y hydrogen adipate having from 2 to 6 carbon atoms and R contains at least r (7) z'stearoyloxy succmlc and monowthyl carbon one alkyl radical having from 16 to 18 carbon atoms. ate) 5. A stearoyloxysuccinyl bis (ethyl carbonate) having 3 Stearoyi i g x fi hydrg6n.succmate' from 1 to 2 stearoyloxy groups per molecule. E 3 g g i ig g succmate 6. Stearoyl propylene glycol succinatyl ethyl carbonate. P y i g 7. Dis-tearin succinatyl ethyl carbonate. 20 No references cited 8. 4-stearoyloxybutyry1 ethyl carbonate. 9. Octadecyl glutaratyl ethyl carbonate. HENRY R. JILES, Primary Examiner. 

